Ruthenium‐Catalyzed Direct Methylation of Primary and Secondary Aromatic Amines Using Carbon Dioxide and Molecular Hydrogen

The effective catalytic N-methylation of anilines using CO2 as C1 source and molecular hydrogen as reducing agent was demonstrated using the well-defined [Ru(triphos)(tmm)] catalyst. Secondary and primary (shown) aromatic amines were mono- or dialkylated, respectively, in high yields. N-methylation of amides coupled with the amide hydrogenation offers an efficient approach to unsymmetrical tertiary methyl/alkyl/aromatic amines.